Crystallization of Lipids

About the EditorKIYOTAKA SATO is Professor Emeritus, Hiroshima University, Japan.

• Preface xiiiList of Contributors xv1 Introduction: Relationships of Structures, Properties, and Functionality 1Kiyotaka Sato1.1 Introduction 11.2 Lipid Species 11.2.1 Hydrocarbons 11.2.2 Fatty Acids 21.2.3 Alcohols and Waxes 41.2.4 Acylglycerols 41.3 Physical States and the Functionality of Lipid Products 51.4 Formation Processes of Lipid Crystals 71.5 Polymorphism 91.6 Aging and Deterioration 111.7 Trans‐Fat Alternative and Saturated‐Fat Reduction Technology 13References 152 Polymorphism of Lipid Crystals 17Kiyotaka Sato2.1 Introduction 172.2 Thermal Behavior of Polymorphic Transformations 172.3 Molecular Properties 202.3.1 Subcell and Chain‐Length Structures 202.3.2 Conformation of Hydrocarbon Chains 242.3.3 Glycerol Conformations 252.3.4 Polytypism 262.4 Fatty Acids 272.4.1 Saturated Fatty Acids 272.4.2 Unsaturated Fatty Acids 322.5 Monoacylglycerols and Diacylglycerols 372.5.1 Crystal/Molecular Structures 372.5.2 Polymorphic Behavior 392.6 Triacylglycerols (TAGs) 412.6.1 Crystal/Molecular Structures 422.6.2 Polymorphic Behavior 462.7 Conclusions 54References 543 Molecular Interactions and Mixing Phase Behavior of Lipid Crystals 61Eckhard Floeter, Michaela Haeupler, and Kiyotaka Sato3.1 Introduction 613.2 Thermodynamic Considerations 633.2.1 Framework for Engineering Calculations 633.2.2 Phase Behavior of Co‐Crystallizing Components 663.2.3 Governing Principles for Phase Boundaries 703.3 Effects of Molecular Structures on the Phase Behavior 703.3.1 Aliphatic Chain‐Chain Interactions: n‐Alkanes 713.3.2 Mixtures of Fatty Acids 723.3.3 Mixtures of Partial Glyceride Fatty‐Acid Esters 813.3.4 Mixtures of TAGs 823.4 Mixing Behavior of TAGs in Natural and Interesterified Fats 923.4.1 Cocoa Butter 933.4.2 Palm Oil 943.4.3 Coconut Oil 953.4.4 Milk Fat 953.4.5 Interesterified Fats 963.5 Crystallization Properties 973.6 Conclusions 98References 1004 Fundamental Aspects of Crystallization of Lipids 105Hironori Hondoh, Satoru Ueno, and Kiyotaka Sato4.1 Introduction 1054.2 Physical and Structural Properties of Lipid Liquids 1054.2.1 Preheating Effects 1064.2.2 Liquid Phases of Triacylglycerols 1094.3 Driving Forces for Crystallization 1124.4 Nucleation 1144.4.1 Homogeneous versus Heterogeneous 1144.4.2 Polymorph‐Dependent Nucleation Kinetics 1184.4.3 Secondary Nucleation 1214.4.4 Crystal Seeding 1224.5 Kinetics of Crystal Growth 1254.5.1 Mechanism of Crystal Growth 1254.5.2 Crystal Growth Rate 1274.5.3 Polymorph‐Dependent Growth Rate 1294.5.4 Spherulite 1304.5.5 Epitaxial Growth 1324.5.6 Morphology of Crystals 1334.6 Conclusions 135Acknowledgment 136References 1365 Supramolecular Assembly of Fat Crystal Networks from the Nanoscale to the Mesoscale 143Fernanda Peyronel, Nuria C. Acevedo, David A. Pink, and Alejandro G. Marangoni5.1 Introduction 1435.2 Cryo‐TEM 1445.2.1 Challenges Associated with the Microscopic Observation of Fat Microstructure 1445.2.2 Sample Preparation for Cryo‐TEM 1455.2.3 Nanoscale Structure Characterization 1465.2.4 Effects of External Fields on Fat Nanostructure 1485.3 Physical Interactions, Models, and Mathematical Methods 1545.3.1 Models in General 1555.3.2 Coarse‐Grained Interactions: Nano‐ to Mesoscale 1565.3.3 Models Using Spheres 1575.3.4 Introduction to Modeling the Statics and Dynamics of Aggregates 1575.3.5 Static Structure Functions 1585.3.6 Application 1: CNP Aggregation. Tristearin Solids in Triolein Oil 1585.3.7 Application 2: Complex Oils. Tristearin Solids in Complex Oils 1615.3.8 Application 3: Nanoscale Phase Separation in Edible Oils 1625.4 Ultra Small Angle X‐Ray Scattering (USAXS) 1645.4.1 Principles of X‐Ray Scattering 1645.4.2 USAXS Instrumentation at the APS 1675.4.3 Sample Preparation 1685.4.4 Unified Fit and Guinier‐Porod Models 1685.4.5 Experimental Results 1705.5 Concluding Remarks 174Acknowledgments 175References 1756 Effects of Dynamic Temperature Variations on Microstructure and Polymorphic Behavior of Lipid Systems 183Laura Bayés‐García, Teresa Calvet, and Miquel À. Cuevas‐Diarte6.1 Introduction 1836.2 Influence on the Polymorphic Behavior in Bulk State 1836.2.1 Single Tag Components 1836.2.2 Binary Mixtures of TAGs 1896.3 Colloidal Dispersion States 1936.3.1 Emulsions 1936.3.2 Organogels 1966.4 Role of Thermal Treatments on End Food Products Properties 1986.4.1 Milk Fats 1986.4.2 Other Dairy Products 1996.4.3 Cocoa Butter 2006.4.4 Vegetable Fats 2046.5 Conclusions 206References 2077 Lipid Crystal Networks Structured under Shear Flow 211Farnaz Maleky and Gianfranco Mazzanti7.1 Introduction 2117.2 Overview of the Formation of Fat Crystals 2127.3 Temperature Gradients and Optimal Supercooling 2137.4 Basic Concepts on Shear Flow 2147.5 Fat Crystallization under Shear 2167.5.1 Shear Affects Polymorphic Transformations 2167.5.2 Crystalline Orientation Induced by Shear Flow 2197.5.3 Shear Affects Fat Structural Properties at the Micro‐ and Nano‐Length Scales 2247.5.4 Physicochemical Properties of Sheared Fat Matrices 2277.5.5 Effects of Shear Flow on Mass Transfer Dynamics of Crystallizing and Crystallized Materials 2317.6 Concluding Remarks 233References 2348 Tailoring Lipid Crystal Networks with High‐Intensity Ultrasound 241Yubin Ye, Peter R. Birkin, and Silvana Martini8.1 Introduction 2418.2 Fundamentals of Sonication 2428.2.1 Acoustic Driving Force 2428.2.2 Acoustic Cell Characteristics 2438.2.3 Cavitation 2448.2.4 Experimental Conditions 2458.3 Tailoring Lipid Crystal Networks 2468.3.1 Crystallization Kinetics 2468.3.2 Inferential Mechanism 2498.3.3 Postsonication Changes 2508.4 Practical Considerations 2558.4.1 Oxidation 2558.4.2 Scale Up 2578.4.3 Combination with Other Processing Methods 2588.5 Conclusions and Future Research 258References 2599 Effects of Foreign and Indigenous Minor Components 263Kevin W. Smith and Kiyotaka Sato9.1 Introduction 2639.2 Basic Understanding 2649.3 Effects of Foreign Components 2659.3.1 Emulsifiers 2659.3.2 Indigenous Minor Components 2769.4 Other Additives 2769.5 Conclusions 278References 27910 Crystallization Properties of Milk Fats 283Christelle Lopez10.1 Introduction 28310.2 Milk Fat: A Wide Diversity of Fatty Acids and Triacylglycerols (TAGs) 28410.3 Crystallization Properties of Bovine Anhydrous Milk Fat (AMF) 28510.3.1 Thermal Properties 28510.3.2 Effect of Cooling Rate on AMF Crystals 28610.3.3 Effect of Shear on AMF Crystals 29510.3.4 Effect of Minor Lipid Compounds 29510.4 Crystallization of TAGs in Bovine Milk Fat Globules and Emulsion Droplets 29610.4.1 Effect of Cooling Rate and Tempering 29810.4.2 Effect of the Size of Milk Fat Globules and Lipid Droplets 30410.5 Crystallization Properties of Milk Fat in Dairy Products 30610.6 Tag Compositions Affecting Crystallization Properties of Milk Fat 30810.6.1 Technological Process: Dry Fractionation 30810.6.2 Dietary Manipulations 31210.6.3 Milk Fat from Various Mammal Species 31510.7 Liquid Tag Phase 31610.8 Conclusions 317References 31811 Crystallization Behavior of Sunflower Oil–Based Fats for Edible Applications 323Maria L. Herrera and Silvana Martini11.1 Introduction 32311.2 High Stearic High Oleic Sunflower Oil 32411.2.1 Fractionation of HSHO‐SFO 32411.2.2 Crystallization Behavior 32611.2.3 Polymorphic Behavior 32911.3 Blends of Sunflower Oil and Milk Fat 33711.3.1 Chemical Composition 34011.3.2 Physical Properties 34011.3.3 Addition of Palmitic Sucrose Ester 34411.4 HSHO‐Based CBE 34711.5 Conclusions 348References 34812 Physical Properties of Organogels Developed with Selected Low‐Molecular‐Weight Gelators 353Jorge F. Toro‐Vazquez, Flor Alvarez‐Mitre, and Miriam Charó‐Alonso12.1 Introduction 35312.2 Basic Aspects of LMOGs: From Molecular Architecture to Functional Assemblies 35512.3 Why Developing Organogels with Vegetable Oils? 35612.3.1 Vegetable Oils as Solvent in the Development of Organogels with LMOGs 35712.3.2 Relationship between Molecular Structure of LMOGs and Physical Properties of Organogels 36712.4 Organogels of Candelilla Wax 37312.4.1 Rheological Properties of Candelilla Wax Organogels Developed Applying Shear Rate 37312.4.2 Applications of Candelilla Wax Organogels 37712.5 Conclusions 377References 37913 Formation and Properties of Biopolymer‐Based Oleogels 385Ashok R. Patel13.1 Introduction 38513.2 Formation of Polymer‐Based Oleogels 38613.2.1 Polymer Oleogelation through Direct Methods 38713.2.2 Polymer Oleogelation through Indirect Methods 38913.3 Properties of Polymer‐Based Oleogels 39313.3.1 Mechanical Properties 39313.3.2 Temperature Sensitivity 39413.3.3 Stability in Presence of Water 39713.4 Potential Applications of Polymer‐Based Oleogels 39713.4.1 Replacement of Beef Fat in Frankfurters 39713.4.2 Heat‐Resistant Chocolates 39713.4.3 Polymer Oleogels as Alternative to Full‐Fat Shortenings 39713.4.4 Bakery Applications of Ethyl Cellulose Oleogels 39813.5 Conclusions: Opportunities and Challenges 398Acknowledgments 401References 40214 Lipid Crystallization in Water‐in‐Oil Emulsions 405Nicole L. Green and Dérick Rousseau14.1 Introduction 40514.2 Basics of Emulsion Properties 40614.3 Emulsifier Effects on W/O Emulsions 40814.3.1 Mono‐ and Diacylglycerols (E471) 40914.3.2 Sucrose Fatty‐Acid Esters (E473) 41114.3.3 Lecithins (E322) 41214.3.4 Sorbitan Esters and Polyesters (E491‐E496) 41314.3.5 Polyglycerol Esters (E475 – E476) 41514.4 Stabilization Modes of W/O Emulsions 41514.4.1 Pickering Stabilization 41614.4.2 Network Stabilization 42014.4.3 Combined Pickering and Network Stabilization 42114.5 Conclusions 423References 42415 Crystallization of Lipids in Oil‐in‐Water Emulsion States 431John N. Coupland15.1 The Basic Concepts 43115.2 Surface Nucleation 43215.3 Polymorphic Transitions in Droplets 43615.4 Morphology of Crystalline Droplets 43715.5 Colloidal Stability of Crystalline Droplets 43915.6 Conclusions 442References 44316 Lipid Crystals and Microstructures in Animal Meat Tissues 447Michiyo Motoyama, Genya Watanabe, and Keisuke Sasaki16.1 Introduction 44716.2 Depot Fat and Crystalline State 44816.2.1 Adipose Tissue 44816.2.2 Triacylglycerol (TAG) Compositions of Animal Fats 44916.3 Fat Crystals and Quality of Porcine Adipose Tissue 45016.3.1 Polymorphism of Extracted Porcine Fat Crystals 45016.3.2 Fat Crystals and Macroscopic Meat Quality 45416.3.3 Application to Actual Meat and Meat Products 45516.4 Crystal Microstructures in Adipose Tissues 46016.5 Concluding Remarks 462Acknowledgments 462References 46217 Conventional and New Techniques to Monitor Lipid Crystallization 465Annelien Rigolle, Koen Van Den Abeele, and Imogen Foubert17.1 Introduction: What Would Be a Perfect Technique? 46517.2 Conventional Techniques (and Advances Made) 46617.2.1 Pulsed Nuclear Magnetic Resonance 46617.2.2 Differential Scanning Calorimetry 46917.2.3 X‐Ray Diffraction 47217.2.4 Rheology 47417.2.5 Microscopy 47617.3 “New” Techniques with Potential for Online Monitoring 47817.3.1 Ultrasonic Techniques 47817.3.2 Laser Backscattering 48417.3.3 Near‐Infrared and Raman Spectroscopy 48517.4 Conclusions 485Acknowledgments 486References 487Index 493